Azo coloring material



Patented July 24, 1934 res PATE T} OFFICE Azo COLORING MATERIAL Fritz Ballaui. and Albert Schmelzer, Cologne- I Mulheim, -Germany, assignors to General M Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application April 20,1932, sonar No. 606,515. In Germany'April25,1931

12 Claims. (01. 260-86) The present invention relates to coloring materials and to materials colored therewith, more particularly it relates to coloring materials which may be represented by the probable general forwherein the benzene nucleus Bz is attached by the positions land 2 to the benzene nucleus Be in an u-fi-PbSllliOIl, R and R stand for hydrocarbon radicals of the aliphatic, 'aromatic or aliphatic-aromatic series, for example, for methyl, ethyl, phenyl and benzyl, one X stands for the hydroxy group and the other X stands for the radicalof a diazo compound suitable for producing an azodyestufi free from a group inducing solubility in water, such as a sulfonic acid and carboxylic acid group, said radical of a diazocompond being attached to the benzene nucleus Bz' by the azo-bridge.

The types of coloring materials falling within follows:

, ducing azodyestuifs free from a group inducing solubility in water, that means fD stands for an'aroma-ticorheterocyclic nucleus, such as a benzene, naphthalene, ldiphenylene-oxide, carba- .hydroxy-benzindole of the general'formula:

zole nucleus which may bear substituents, such as alkyl, alkoxy,the nitro groupand halogen. The coupling components of the benzindole series used in our invention are obtainable for example from the correspondingbenzindole sulionic acids by alkali fusion. The benzindole sulfonic acids again can be ,prepared according to known methods,. for example, by transforming the hydrazinesof the corresponding naphthyl: amino-sulfonic acids, that are 1- or- Z-naphthalene-6-"or 7-sulfonicacid, into. ketone hydrazones by means of a suitable; ketone, such as acetone, diethyl-ketone, ethyl-methyl ketone, acetophenone, ethyl-phenyl ketone, and eflect ing the synthesis of. the indole'by heating with 9 an acid condensing agentQ fI'he 2.3-diphenyl- .hydroxy-benzindole'ssuitable for our invention have been described in our U. S. Patent No. 1,906,221, dated SeptemberBO, 1932.

Our new coloring materials are obtainable 8.0- 7 5 cording .to known methods by diazotizing a primary amine suitable ior producing an azodyestuil? free from a group inducing solubility in water and coupling in substance or on the fibre with a examples, without being limited thereto:

" Example 1.Well boiled and dried cotton is impregnated with'a solution of 5 grams of 8- B. caustic soda and 10 cos. of Turkey red oil per hydroxy-2-phenyl a naphthindole, 10 cos. of 34 ,105 litre, wrung out and developed without the necessity of drying in a diazo solution neutralized with sodium acetate and containing 1.7 grams per litre of:2.5-dichloroaniline,rinsed and soaped. In this manner is obtained a beautiful, fast reddish yields, for example, with: Y 2 methyl 4-nitrani1ine a dark brown brown. The coloring material corresponds to the following formula:

The following list gives several further combinations, obtainable in a manner analogous to that described in the above example together with the corresponding shades:-

8 hydroxy 2 phenyl-u-naphthindole yields with: 2-:chloroaniline a reddish brown with a a l a yellowish tinge 2-methyl-5-chloroaniline- -a reddish violet 4-chloro- 2-nitraniline -a deep reddish brown a-naphthylamine a deep reddish brown Similar shades are obtained when using instead of 8 -hydroxy,-Z-phenyl-a-naphthindole the corresponding 8-hydroxy-2 phenyl- 3+naphthindole. Example 2.3,5 grams of 8 hydroxy-2-pheny1- -naphthindole are dissolved in water with the addition of caustic soda, and to this solution there is added a diazo solution prepared in the usual manner from 1,5, grams of 2.5-dichloroaniline. n rendering the reaction of the solution acetic acid by the addition of sodium acetate coupling enters and the coloring material which is identical with that described in Example Lparagraph l,

precipitates. It is filtered and dried and represents a valuable pigment.

l a i i The following listgives several further combinations obtainable in a manner analogous to "that described in the above example together with the corresponding shades:

f8 hydroiiy 2.3' dimethyl n; naphthindole of a violet tinge 2,-methyll -ch1oroanilinm a dark reddish brown Similar shades can be obtained, for eirample,

from 8-hydroxy-2.3-methylethyl-a-naphthindole and 8-hydroxy-2.3-diphenyl-a-naphthindole.

Example 4.Well boiled and dried cotton is impregnated with a solution of 5 grams of 7-hydroxy-2.3-dimethylnaphthindole,' 10 cos. of 34 B. caustic soda lye and 10 cos. of Turkey red oil per litre, wrung out and developed, without the necessity of drying, in a diazo solution, neu- :tralized by means of sodium acetate, containing 1.7 grams per litre of 2.5-dichloroaniline, rinsed and soaped. In this manner a beautiful, dark reddish brown is obtained. The coloring material corresponds to the following formula:

and"

From 7-hydroxy-2-phenylnaphthindole of the general 10 wherein the benzene nucleus Bz is. attached by the positions 1 and'2 to the benzene nucleus B2 in an e s-position,'-R. and R' stand for hydrocarbon radicalsof the aliphatic, phenyl or benzyl series, one X stands for the hydroxy group and the other X stands for the radical of an aromatic diazo compound suitable for produc-' ing an azodyestuff free from a group inducing solubility in water, said radical ,of an aromatic diazo compound being attachedto the benzene nucleus Bz. by the azo-bridge, yielding, when produced on the fibre, generally brown shades of good fastness properties. 7

2. The coloring materials of the general formula: 1

its

compound-suitable for producing an azodyestufi free from a group inducing solubility in water, said radical of an aromatic diazo compound'being attached to the benzene nucleus Bz by the azo-bridge, yielding, when produced on the fibre, generally brown shades of good fastness properties.

3. The coloring materials of the general formula:

it Bl Bz H wherein R and R' stand for hydrocarbon radicals of the aliphatic, phenyl or benzyl series, one X stands for the hydroxy group and the other X stands for the radical of an aromatic diazo compound of the benzene or naphthalene series in which the nuclei may be substituted by substituents selected from the group consisting of halogen, alkyl, alkoxy and the nitro group, said radical of an aromatic diazo compound being attached to the benzene nucleus 32' by the azo-bridge, yielding, when produced on the fibre, generally brown shades of good fastness properties.

4. The coloring materials of the general formula:

wherein R and R stand for hydrocarbon radicals of the aliphatic, phenyl or benzyl series, D stands for a benzene or naphthalene nucleus which may be substituted by substituents selected from the group consisting of halogen, alkyl, alkoxy and the nitro group, yielding, when produced on the fibre, generally brown shades of good fastness properties.

5. The coloring material of the following formula:

yielding, when produced on the fibre, reddish 9o brown shades of good fastness properties.

6. The coloring material of the following formula: 

